This study concerns understanding of the underlying mechanistic pathways in high temperature Solution polymerization of n-butyl acrylate (nBA) in the absence of added thermal initiators. The particular system of interest is the batch polymerization of nBA in xylene at temperatures between 140 and 180 degrees C with initial monomer content between 20 and 40 wt%. A mechanistic process model is developed to capture the dynamics of the polymerization system. Postulated reaction mechanisms include chain-initiation by monomer (self-initiation). chain-initiation by unknown impurities, chain-propagation by secondary and tertiary radicals, intra-molecular chain-transfer to polymer (back-biting), chain-fragmentation (beta-scission), chain-transfer to monomer and solvent, and chain termination by disproportionation and combination. The extent of the reactions is quantified by estimating the reaction rate constants of the initiation and the secondary reactions, based on a set of process measurements. The set of measurements considered in the parameter estimation includes monomer conversion, number- and weight-average molecular weights, and average number of chain-branches per chain (CBC). Effect of temperature on chain microstructures was observed to be most evident when microstructures are expressed in terms of their quantities per chain. The evolution of other microstructural quantities such as average number of terminal double bonds per chain (TDBC) and average number of terminal solvent groups per chain (TSGC) was then also investigated. Microstructural quantities per polymer chain (TDBC, TSGC, CBC) are defined based on combinations of C-13. H-1 NMR and chromatographic measurements. This study presents (i) a mechanistic explanation for the competing nature Of Short-chain-branch and terminal double bond formation (i.e. as temperature increases, number of chain branches per chain decreases and number of terminal double bonds per chain increases), (ii) quantitative insights into dominant modes of chain-initiation and chain-termination reactions, and (iii) mechanistic explanations for the observed spontaneous polymerization. The study also reports estimated Arrhenius parameters for second-order self initiation, tertiary radical propagation, secondary radical backbiting and tertiary radical P-scission reaction rate constants. Validation of the mechanistic process model with the estimated Arrhenius parameters and comparison of estimated parameter values to recently reported estimates are also presented. (c) 2005 Elsevier Ltd. All rights reserved.